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EP1694754A1 - Piece moulee en mousse particulaire composee de granules polymeres expansibles contenant une charge - Google Patents

Piece moulee en mousse particulaire composee de granules polymeres expansibles contenant une charge

Info

Publication number
EP1694754A1
EP1694754A1 EP04803476A EP04803476A EP1694754A1 EP 1694754 A1 EP1694754 A1 EP 1694754A1 EP 04803476 A EP04803476 A EP 04803476A EP 04803476 A EP04803476 A EP 04803476A EP 1694754 A1 EP1694754 A1 EP 1694754A1
Authority
EP
European Patent Office
Prior art keywords
expandable
range
filler
weight
thermoplastic polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04803476A
Other languages
German (de)
English (en)
Inventor
Klaus Hahn
Gerd Ehrmann
Joachim Ruch
Markus Allmendinger
Bernhard Schmied
Klaus MÜHLBACH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1694754A1 publication Critical patent/EP1694754A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3461—Making or treating expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene

Definitions

  • Particle foam molded parts made of expandable polymer granules containing filler
  • the invention relates to particle foam molded parts with a density in the range from 8 to 200 g / l, which can be obtained by welding pre-expanded foam particles made of expandable, filler-containing, thermoplastic polymer granules, and to processes for producing the expandable polymer granules.
  • Expanded and expandable styrene polymers can also be produced by means of extrusion processes.
  • the blowing agent is e.g. mixed into the polymer melt via an extruder, conveyed through a nozzle plate and granulated into particles or strands (US Pat. No. 3,817,669, GB 1,062,307, EP-B 0 126459, US Pat. No. 5,000,891).
  • EP-A 668 139 describes a process for the economical production of expandable polystyrene granules (EPS), the blowing agent-containing melt being produced by means of static mixing elements in a dispersion, holding and cooling stage and then being granulated. Due to the cooling of the melt to a few degrees above the solidification temperature, high amounts of heat have to be removed.
  • EPS expandable polystyrene granules
  • GB 1 048 865 describes polystyrene extrusion foams with a high filler content in the form of sheets, strips and tapes with densities in the range from 100 to 1100 kg / m 3 .
  • Polystyrene containing blowing agents is premixed with the fillers and put in an extruder. Expandable styrene and polystyrene particle foams with a high filler content are not described.
  • WO 03/035728 describes the production of expandable polystyrene, which is an inorganic filler with an average diameter in the range from 0.01 to 100 ⁇ m, a refractive index above 1.6 and a color index of 22 or below.
  • 1 to 4% by weight of TiO 2 are used as a replacement for IR absorbers, such as graphite, in order to reduce the thermal conductivity of the foams.
  • Expandable styrene polymers containing halogen-free flame retardants are known. According to EP-A 0 834 529, at least 12% by weight of a mixture of a phosphorus compound and a water-releasing metal hydroxide, for example triphenyl phosphate and magnesium hydroxide, is used as the flame retardant in order to obtain foams which pass the fire test B2 in accordance with DIN 4102.
  • a water-releasing metal hydroxide for example triphenyl phosphate and magnesium hydroxide
  • WO 00/34342 describes expandable styrene polymers which contain 5 to 50% by weight of expandable graphite as flame retardant and optionally 2 to 20% by weight of a phosphorus compound.
  • WO 98/51735 describes expandable styrene polymers containing graphite particles with reduced thermal conductivity, which can be obtained by suspension polymerization or by extrusion in a twin-screw extruder. As a result of the high shear forces in a twin-screw extruder, a significant decrease in the molecular weight of the polymer used and / or partial decomposition of added additives, such as flame retardants, are generally observed.
  • EPS expandable styrene polymer
  • EPS granules produced by extrusion often cannot be foamed into foams with an optimal foam structure.
  • EP-A 1 002 829 describes the suspension polymerization of styrene in the presence of silylated glass fibers to give EPS particles which are processed into an open-cell foam.
  • particle foam molded parts obtainable by welding pre-expanded foam particles made of expandable, filler-containing, thermoplastic polymer granules, were found, the particle foam having a density in the range from 8 to 200 g / l, preferably in the range from 10 to 50 g / l.
  • the particle foam molded parts according to the invention despite the presence of fillers, have a high closed-cell structure, with generally more than 60%, preferably more than 70, particularly preferably more than 80% of the cells of the individual foam particles being closed-celled.
  • Suitable fillers are organic and inorganic powders or fibrous materials, and also mixtures thereof.
  • organic fillers such.
  • wood flour, starch, flax, hemp, ramie, jute, sisal, cotton, cellulose or aramid fibers can be used.
  • inorganic fillers such.
  • carbonates, silicates, heavy latex, glass spheres, zeolites or metal oxides can be used.
  • Powdery inorganic substances such as talc, chalk, kaolin (Al 2 (Si 2 O 5 ) (OH)), aluminum hydroxide, magnesium hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, calcium sulfate, silica, quartz powder, aerosil, are preferred.
  • Alumina or wollastonite or spherical or fibrous, inorganic substances such as glass spheres, glass fibers or carbon fibers.
  • the average particle diameter or, in the case of fibrous fillers, the length should be in the range of the cell size or smaller.
  • Inorganic fillers with a density in the range from 2.0 to 4.0 g / cm 3 are particularly preferred, in particular in the range from 2.5 to 3.0 g / cm 3 .
  • the whiteness / brightness (DIN / ISO) is preferably 50-100%, in particular 70-98%.
  • the oil number according to ISO 787/5 of the preferred fillers is in the range from 2 to 200 g / 100 g, in particular in the range from 5 to 150 g / 100 g
  • the type and amount of the fillers can influence the properties of the expandable thermoplastic polymers and the particle foam molded parts obtainable therefrom.
  • the proportion of the filler is generally in the range from 1 to 50, preferably 5 to 30,% by weight, based on the thermoplastic polymer.
  • adhesion promoters such as maleic anhydride-modified styrene copolymers, polymers containing epoxy groups, organosilanes or styrene copolymers with isocyanate or acid groups, the connection of the filler to the polymer matrix and thus the mechanical properties of the particle foam molded parts can be significantly improved.
  • inorganic fillers reduce flammability.
  • the fire behavior can be significantly improved, in particular by adding inorganic powders such as aluminum hydroxide.
  • thermoplastic polymer granules according to the invention show a low loss of blowing agent during storage even at high filler contents. Due to the nucleating effect, a reduction in the blowing agent content, based on the polymer, is also possible.
  • thermoplastic polymers which can be used are styrene polymers, polyamides (PA), polyolefins, such as polypropylene (PP), polyethylene (PE) or polyethylene-propylene copolymers, polyacrylates, such as polymethyl methaceylate (PMMA), polycarbonate (PC), polyesters, such as polyethylene terephthalate (PET ) or polybutylene terephthalate (PBT), polyether sulfones (PES), polyether ketones or polyether sulfides (PES) or mixtures thereof.
  • Styrene polymers are particularly preferably used.
  • the expandable styrene polymer preferably has a molecular weight in the range from 190,000 to 400,000 g / mol, particularly preferably in the range from 220,000 to 300,000 g / mol. Due to the reduction in molecular weight due to shear and / or the effect of temperature, the molecular weight of the expandable polystyrene is generally about 10,000 g / mol below the molecular weight of the polystyrene used.
  • the strand expansion after the nozzle outlet should be as small as possible. It has been shown that the strand expansion can be influenced, inter alia, by the molecular weight distribution of the styrene polymer.
  • the expandable styrene polymer should therefore preferably have a molecular weight distribution with a non-uniformity M w / M n of at most 3.5, particularly which preferably have in the range from 1.5 to 2.8 and very particularly preferably in the range from 1.8 to 2.6.
  • Preferred styrene polymers are glass-clear polystyrene (GPPS), impact-resistant polystyrene (HIPS), anionically polymerized polystyrene or impact-resistant polystyrene (A-IPS), styrene-a-methstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile (SAN) Acrylonitrile-styrene-acrylic ester (ASA), methacrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) - polymers or mixtures thereof or with polyphenylene ether (PPE).
  • GPPS glass-clear polystyrene
  • HIPS impact-resistant polystyrene
  • A-IPS anionically polymerized polystyrene or impact-
  • the styrene polymers mentioned can be used, if appropriate, using compatibilizers with thermoplastic polymers, such as polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethyl methacrylate (PMMA), Polycarbonate (PC), polyesters, such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyether sulfones (PES), polyether ketones or polyether sulfides (PES) or mixtures thereof, as a rule in proportions of up to a maximum of 30% by weight, are preferred in the range from 1 to 10% by weight, based on the polymer melt, are mixed.
  • thermoplastic polymers such as polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethyl methacrylate (PMMA), Polycarbonate (PC), polyesters, such as polyethylene terephthalate
  • mixtures in the stated ranges are also with z.
  • B hydrophobically modified or functionalized polymers or oligomers, rubbers, such as polyacrylates or polydienes, eg. B. styrene-butadiene block copolymers or biodegradable aliphatic or aliphatic / aromatic copolyesters are possible.
  • Suitable compatibilizers are e.g. Maleic anhydride-modified styrene copolymers, polymers containing epoxy groups or organosilanes.
  • Polymer recyclates of the abovementioned thermoplastic polymers in particular styrene polymers and expandable styrene polymers (EPS), can also be mixed into the styrene polymer melt in amounts which do not significantly impair their properties, generally in amounts of at most 50% by weight, in particular in amounts of 1 to 20 wt .-%.
  • EPS expandable styrene polymers
  • the blowing agent-containing styrene polymer melt generally contains one or more blowing agents in a homogeneous distribution in a proportion of a total of 2 to 10% by weight, preferably 3 to 7% by weight, based on the blowing agent-containing styrene polymer melt.
  • Suitable blowing agents are the physical blowing agents usually used in EPS, such as aliphatic hydrocarbons with 2 to 7 carbon atoms, alcohols, ketones, ethers or halogenated hydrocarbons. Iso-butane, n-butane, iso-pentane, n-pentane is preferably used.
  • finely divided interior water droplets can be introduced into the styrene polymer matrix. This can be done, for example, by adding water to the melted styrene polymer matrix. The water can be added locally before, with or after the propellant metering. A homogeneous distribution of the water can be achieved using dynamic or static mixers.
  • 0 to 2 preferably 0.05 to 1.5% by weight of water, based on the styrene polymer, is sufficient.
  • Expandable styrene polymers with at least 90% of the internal water in the form of internal water droplets with a diameter in the range from 0.5 to 15 ⁇ m form foams with a sufficient number of cells and a homogeneous foam structure when foamed.
  • the amount of blowing agent and water added is selected so that the expandable styrene polymers (EPS) have an expansion capacity ⁇ , defined as bulk density before foaming / bulk density after foaming, at most 125, preferably 25 to 100.
  • EPS expandable styrene polymers
  • the expandable styrene polymer granules (EPS) according to the invention generally have a bulk density of at most 700 g / l, preferably in the range from 590 to 660 g / l.
  • bulk densities in the range from 590 to 1200 g / l can occur.
  • the styrene polymer melt can also contain additives, nucleating agents, plasticizers, flame retardants, soluble and insoluble inorganic and / or organic dyes and pigments, e.g. IR absorbers, such as carbon black, graphite or aluminum powder, together or spatially separated, e.g. can be added via mixer or side extruder.
  • IR absorbers such as carbon black, graphite or aluminum powder
  • the dyes and pigments are added in amounts in the range from 0.01 to 30, preferably in the range from 1 to 5,% by weight.
  • a dispersing aid e.g. Organosilanes, polymers containing epoxy groups or styrene polymers grafted with maleic anhydride.
  • Preferred plasticizers are mineral oils, low molecular weight styrene polymers, phthalates, which can be used in amounts of 0.05 to 10% by weight, based on the styrene polymer.
  • an IR absorber such as carbon black or graphite is preferably used in amounts of 0.1 to 10% by weight, in particular in amounts of 2 to 8% by weight.
  • carbon black when using smaller amounts of fillers, e.g. B. below 5 wt .-%, it is also possible to use carbon black in amounts of 1 to 25 wt .-%, preferably in the range of 10 to 20 wt .-%. At these high carbon black contents, the carbon black addition is preferably mixed into the styrene polymer melt by means of the mainstream and a side-stream extruder.
  • soot agglomerates to be simply comminuted to an average agglomerate size in the range from 0.3 to 10 / m, preferably in the range from 0.5 to 5 ⁇ m, and homogeneous coloring of the expandable styrene polymer granules which form closed-cell foam particles with a Density in the range of 5 -40 kg / m 3 , in particular 10 - 15 kg / m 3 can be foamed.
  • the particle foams obtainable with 10 to 20% by weight carbon black after foaming and sintering achieve a thermal conductivity ⁇ , determined at 10 ° C according to DIN 52612, in the range from 30 to 33 mW / mK.
  • the BET surface area is preferably in the range from 10 to 120 m 2 / g.
  • Graphite with an average particle size in the range from 1 to 50 ⁇ m is preferably used as graphite.
  • Expandable, styrene polymer granules with reduced thermal conductivity preferably contain
  • a filler selected from powdery inorganic substances such as talc, chalk, kaolin, aluminum hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, titanium dioxide, chalk, calcium sulfate, kaolin, silica, quartz powder, aerosil, alumina or wollastonite and
  • the EPS granules particularly preferably contain hexabromocylododecane (HBCD) as the flame retardant and dicumyl or dicumyl peroxide as the flame retardant synergist.
  • HBCD hexabromocylododecane
  • the weight ratio of flame retardant synergist to organic bromine compound is generally in the range from 1 to 20, preferably in the range from 2 to 5.
  • carbonates, such as chalk, as fillers the hydrogen halide acids released by halogenated flame retardants, such as HBDC, are neutralized and the corrosion of plants during processing is avoided or reduced.
  • a filler selected from powdery inorganic substances such as talc, chalk, kaolin, aluminum hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, titanium dioxide, chalk, calcium sulfate, kaolin, silica, quartz powder, areosil, alumina or wollastonite and
  • Preferred halogen-free, flame-retardant expandable styrene polymer granules contain, in addition to the fillers and expandable graphite, 1 to 10% by weight of red phosphorus, triphenyl phosphate or 9,10-dihydro-9-oxa-10phospha-phenantrene-10-oxide and an effective IR absorber Expandable graphite different graphite with an average particle size in the range of 0.1 to 100 microns in amounts of 0.1 to 5 wt .-%, each based on styrene polymer.
  • graphite Due to its layered lattice structure, graphite is able to form special forms of intercalation compounds. In these so-called interstitial compounds, foreign atoms or molecules, some of which are stoichiometric, have been incorporated into the spaces between the carbon atoms. These graphite compounds, for example with sulfuric acid as a foreign molecule, which are also produced on an industrial scale, are referred to as expanded graphite.
  • the density of this expanded graphite is in the range from 1.5 to 2.1 g / cm 3 , the average particle size is generally advantageously from 10 to 1000 ⁇ m, in the present case preferably from 20 to 500 ⁇ m and in particular from 30 to 300 ⁇ m ,
  • Inorganic or organic phosphates, phosphites or phosphonates and red phosphorus can be used as phosphorus compounds.
  • Preferred phosphorus compounds are, for example, diphenyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, ammonium polyphosphate, resorcinol diphenyl phosphate, melamine phosphate, dimyl phenyl phosphate or dimethyl methyl phosphonate.
  • the blowing agent is mixed into the polymer melt.
  • the process comprises the steps a) melt production, b) mixing c) cooling d) conveying and e) granulating.
  • Static or dynamic mixers for example extruders, are suitable for mixing.
  • the polymer melt can be removed directly from a polymerization reactor or can be produced directly in the mixing extruder or in a separate melt extruder by melting polymer granules.
  • the melt can be cooled in the mixing units or in separate coolers.
  • Apparatus arrangements suitable for carrying out the method are, for example:
  • the blowing agent-containing styrene polymer melt is generally conveyed through the nozzle plate at a temperature in the range from 140 to 300 ° C., preferably in the range from 160 to 240 ° C. It is not necessary to cool down to the glass transition temperature range.
  • the nozzle plate is heated to at least the temperature of the blowing agent-containing polystyrene melt.
  • the temperature of the nozzle plate is preferably in the range from 20 to 100 ° C. above the temperature of the polystyrene melt containing blowing agent. This prevents polymer deposits in the nozzles and guarantees trouble-free granulation.
  • the diameter (D) of the nozzle bores at the nozzle outlet should be in the range from 0.2 to 1.5 mm, preferably in the range from 0.3 to 1.2 mm, particularly preferably in the range from 0.3 to 0.8 mm. In this way, even after strand expansion, pellet sizes below 2 mm, in particular in the range from 0.4 to 1.4 mm, can be set in a targeted manner.
  • the strand expansion can be influenced by the nozzle geometry.
  • the nozzle plate preferably has bores with a ratio L / D of at least 2, the length (L) denoting the nozzle area, the diameter of which corresponds at most to the diameter (D) at the nozzle outlet.
  • the L / D ratio is preferably in the range from 3 to 20.
  • the diameter (E) of the holes at the nozzle inlet of the nozzle plate should be at least twice as large as the diameter (D) at the nozzle outlet.
  • the nozzle plate has bores with a conical inlet and an inlet angle ⁇ of less than 180 °, preferably in the range from 30 to 120 °. In a further embodiment, the nozzle plate has bores with a conical outlet and an outlet angle ⁇ less than 90 °, preferably in the range from 15 to 45 °.
  • the nozzle plate can be equipped with holes of different outlet diameters (D). The various embodiments of the nozzle geometry can also be combined with one another.
  • a particularly preferred method for producing expandable styrene polymers comprises the steps
  • step g) the granulation can take place directly behind the nozzle plate under water at a pressure in the range from 1 to 25 bar, preferably 5 to 15 bar.
  • Variable back pressure in the UWG enables the targeted production of both compact and foamed granules. Even when using nucleating agents, foaming at the UWG nozzles remains controllable.
  • pressurized underwater pelletizing with pressures in the range from 1 to 40 bar, in particular in the range from 4 to 20 bar, solves the problem.
  • the foaming of the granules can not only be completely suppressed in the presence of nucleating agents (compact granules), but can also be controlled in a targeted manner (slightly foamed granules, bulk density 40 to 550 g / l).
  • the foam is pre-foamed in flowing steam to form foam beads with a density of usually 10-50 kg / m 3, temporarily stored for 24 hours and then welded in gas-tight forms with water vapor to form foam bodies.
  • foaming can be carried out several times in this way, the granules usually being stored temporarily between the foaming steps and possibly being dried.
  • the foamed, dry granules can be further foamed in water vapor or a gas mixture which contains at least 50% by volume of water, preferably at temperatures in the range from 100 to 130 ° C. on even lower poets.
  • the targeted bulk densities are less than 25g / l, in particular between 8 and 16g / l.
  • a polymer melt is directly available for the blowing agent impregnation in stage c) and it is not necessary to melt styrene polymers.
  • This is not only more economical, but also leads to expandable styrene polymers (EPS) with low styrene monomer contents, since the mechanical shearing action in the melting area of an extruder, which usually leads to the cleavage of monomers, is avoided.
  • EPS expandable styrene polymers
  • Shear rates below 50 / sec, preferably 5 to 30 / sec, and temperatures below 260 ° C. and short residence times in the range from 1 to 20, preferably 2 to 10 minutes in stages c) to e) are therefore particularly preferred.
  • Static mixers and static coolers are particularly preferably used in the entire process.
  • the polymer melt can by pressure pumps, for. B. Gear pumps are promoted and carried out.
  • a further possibility for reducing the styrene monomer content and / or residual solvents such as ethylbenzene is to provide a high degassing by means of entraining agents, for example water, nitrogen or carbon dioxide, in stage b) or to carry out the polymerization stage a) anionically.
  • entraining agents for example water, nitrogen or carbon dioxide
  • the anionic polymerization of styrene not only leads to styrene polymers with a low styrene monomer content, but also to a low styrene oligomer content.
  • the finished expandable styrene polymer granules can be coated with glycerol esters, antistatic agents or anti-adhesive agents.
  • the expandable styrene polymer granules (EPS) according to the invention generally have higher bulk densities, which are generally in the range from 590 to 1200 g / l.
  • the expandable thermoplastic polymer granules according to the invention show good expansibility even at low blowing agent contents. Even without a coating, the bond is significantly less than with conventional EPS beads.
  • the expandable, styrene polymer granules according to the invention can be prefoamed by means of hot air or steam to form foam particles with a density in the range from 8 to 200 kg / m 3 , preferably in the range from 10 to 50 kg / m 3 , and then welded in a closed form to give foam moldings.
  • foam particles with a density in the range from 8 to 200 kg / m 3 , preferably in the range from 10 to 50 kg / m 3 , and then welded in a closed form to give foam moldings.
  • n-Pentane based on the total polymer melt
  • Kaolin Kaolin B22, Blancs Mineraux
  • Micro glass balls Micro glass balls PA, Potters-Ballotini GmbH
  • the melt mixture containing blowing agent was cooled in the cooler from originally 260 to 190 ° C.
  • a filler-containing polystyrene melt was metered in via a side-stream extruder, so that the proportion by weight given in Table 1 for the respective filler, based on the granules, was established.
  • the filler-containing polystyrene melt was conveyed at a throughput of 60 kg / h through a nozzle plate with 32 bores (diameter of the nozzle 0.75 mm). With the help of a pressurized underwater pelletizer, compact granules with a narrow size distribution were produced.
  • the pentane contents in the granules measured after the granulation and after 14 days of storage are shown in Table 1
  • the molded foam body was flame-treated with a Bunsen burner flame for 2 seconds. While the molded foam body produced from the comparison test burned off, the molded foam body obtained from Example 17 was self-extinguishing.
  • the pre-expanded beads were passed through a coarse mesh sieve and the proportion remaining in the sieve was determined.
  • Examples 1a, 5a, 7a and 14a were carried out in accordance with Examples 1, 5, 7 and 14, but with the addition of 1% by weight of a styrene-maleic anhydride copolymer with 12% by weight of maleic anhydride (Dylark®) as adhesion promoters.
  • Table 4 shows the compressive strengths of the foam molded articles.
  • the mixture of polystyrene melt, blowing agent, flame retardant and synergist was conveyed at 60 kg / h through a nozzle plate with 32 holes (diameter of the nozzle 0.75 mm). With the help of a pressurized underwater pelletizer, compact granules with a narrow size distribution were produced.
  • VZ viscosity number
  • VZ viscosity number
  • the mixture of polystyrene melt, blowing agent and filler was conveyed at 60 kg / h through a nozzle plate with 32 holes (diameter of the nozzle 0.75 mm). With the help of a pressurized underwater pelletizer (12 bar), compact pellets with a narrow size distribution were produced.
  • VZ viscosity number
  • the mixture of polystyrene melt, blowing agent and filler was conveyed at 60 kg / h through a nozzle plate with 32 holes (diameter of the nozzle 0.75 mm). With the help of pressurized underwater granulation (4 bar), foamed granules (380 kg / m 3 ) with a narrow size distribution were produced.
  • a polystyrene melt was added via a side-stream extruder, which melt contained the fillers (chalk) listed in Table 1 and the corresponding flame retardant mixture (expanded graphite: ES 350 F5 from Kropfmühl , red phosphorus, triphenyl phosphate (TPP) or, 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOP)) and mixed into the main stream.
  • the stated amounts in% by weight relate to the total amount of polystyrene.
  • the mixture of polystyrene melt, blowing agent, filler and flame retardant was conveyed at 60 kg / h through a nozzle plate with 32 holes (diameter of the nozzle 0.75 mm). With the help of pressurized underwater granulation, compact granules with a narrow size distribution were produced.
  • test specimens were stored for at least 72 hours. Examples 1-4 were self-resolving and passed fire test B2 according to DIN 4102.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

L'invention concerne des pièces moulées en mousse particulaire présentant une densité de 8 à 200 g/L, pouvant être obtenues par soudage de particules de mousse prémoussées, composées de granulés polymères thermoplastiques expansibles, contenant une charge. L'invention concerne également des procédés de fabrication de granulés polymères expansibles.
EP04803476A 2003-12-12 2004-12-03 Piece moulee en mousse particulaire composee de granules polymeres expansibles contenant une charge Withdrawn EP1694754A1 (fr)

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Application Number Priority Date Filing Date Title
DE10358786A DE10358786A1 (de) 2003-12-12 2003-12-12 Partikelschaumformteile aus expandierbaren, Füllstoff enthaltenden Polymergranulaten
PCT/EP2004/013748 WO2005056653A1 (fr) 2003-12-12 2004-12-03 Piece moulee en mousse particulaire composee de granules polymeres expansibles contenant une charge

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EP1694754A1 true EP1694754A1 (fr) 2006-08-30

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DE10358786A1 (de) 2005-07-14
WO2005056653A1 (fr) 2005-06-23
CN1890309A (zh) 2007-01-03
SG149017A1 (en) 2009-01-29
US20070112082A1 (en) 2007-05-17
UA79410C2 (en) 2007-06-11
BRPI0417385A (pt) 2007-04-10
RU2006124972A (ru) 2008-01-27
JP2007514027A (ja) 2007-05-31
CA2547888A1 (fr) 2005-06-23
KR20060120195A (ko) 2006-11-24
CN100412118C (zh) 2008-08-20
MXPA06006499A (es) 2006-08-23
RU2371455C2 (ru) 2009-10-27

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